The present invention relates to a method for retrofitting a conventional hydrogen evolving cathode cell to a gas diffusion electrode cell. The invention also relates to the retrofitted electrolytic cell and the use thereof.
The electrolytic production of alkali metal hydroxides is today of considerable importance, although a large amount of energy is consumed in the electrolysis processes. Many attempts have been made to lower the energy consumption, e.g. by using a gas diffusion cathode in the electrolytic cell which today is believed to have the highest capability of saving electric energy and lower the production costs.
If the production of sodium hydroxide from brine in a conventional hydrogen evolving cathode cell in which the electrolytic reaction (1) occurs instead is performed in a gas diffusion cathode cell, the reaction (1) is replaced by reaction (2).
2NaCl+2H2Oxe2x86x92Cl2+2NaOH+H2, E0=2.21 Vxe2x80x83xe2x80x83(1)
2NaCl+xc2xdO2+H2Oxe2x86x92Cl2+2NaOH, E0=0.96 Vxe2x80x83xe2x80x83(2)
Thus, by converting a hydrogen evolving cathode cell to a gas diffusion electrode cell, the cell voltage is reduced from 2.21 V to 0.96 V, thus an energy saving of about 60% becomes possible. Accordingly, various investigations have been conducted for converting conventional cells for production of e.g. chloralkali electrolysis to gas diffusion electrode cells.
U.S. Pat. No. 5,693,213 describes briefly a method for converting a conventional salt water electrolytic cell provided with a conventional hydrogen evolving cathode to a gas diffusion cathode cell in which the cathode chamber is partitioned into a solution chamber and a gas chamber by providing a gas diffusion cathode to the original cell. However, this conversion requires a large reconstruction cost due to the complicated cathode chamber structure needed for controlling the pressure arisen between the gas diffusion electrode and the ion exchange membrane.
The present invention intends to solve the above-mentioned problems.
The present invention relates to a method for retrofitting an electrolytic cell comprising an anode and a cathode compartment, a separator partitioning the compartments, said cathode compartment comprising a hydrogen evolving cathode, wherein the method comprises making at least one substantially horizontal slit in the hydrogen evolving cathode resulting in plural cathode members, bending the edge of the cathode member at the slit away from the separator, arranging a gas diffusion electrode to at least one of the cathode members on the side facing the separator, and arranging an electrolyte layer to the gas diffusion electrode.
It has been surprisingly found that the present invention can provide advantageous operation to a retrofitted gas diffusion electrode cell. The invention enables a simple retrofitted gas diffusion electrode cell by converting a conventional hydrogen evolving cathode cell at a low cost. The invention further ascertains low cell voltage and stable operation. It can thus enable homogeneous connection between the separator and the gas diffusion electrode. The relatively short distance between the separator and the gas diffusion electrode minimises the cell voltage and makes the cell operation almost as energy-saving as a zero gap cell. The invention also ascertains a safe operation minimising flooding of electrolyte in the cathode compartment.
By xe2x80x9cretrofitting an electrolytic cellxe2x80x9d is generally meant equipping or converting an already existing electrolytic cell with new parts.
By the term xe2x80x9cseparatorxe2x80x9d is meant any separating mean, such as an ion exchange membrane, a diaphragm or other suitable means. Suitable membranes may be made of perfluorinated, sulphonated or teflon-based polymers, or ceramics. Also polystyrene-based membranes or diaphragm of polymers or ceramics may be used. There are several commercially available membranes suitable for use such as Nafion(trademark) 324, Nafion(trademark) 550 and Nafion(trademark) 961 available from Du Pont, and Flemion(trademark) available from Asahi Glass.
By the term xe2x80x9cslitxe2x80x9d is meant a long straight incision or opening, suitably a through-line, in the hydrogen evolving cathode.
According to one embodiment, the distance between the slits is from about 100 to about 600 mm, preferably from about 200 to about 400 mm. The slits suitably are from about 2 to 10 mm, preferably from about 3 to about 5 mm wide. The edge of the cathode member can be bent in any direction as long as it allows the electrolyte layer to pass through the slit, but preferably, the edge is bent downwards away from the separator.
By the terms xe2x80x9cexisting cathodexe2x80x9d and xe2x80x9ccathode membersxe2x80x9d is meant any originally existing hydrogen evolving cathode or members of an existing hydrogen evolving cathode used in a conventional electrolytic cell.
By the term xe2x80x9celectrolyte layerxe2x80x9d is meant a hydrophilic layer capable of retaining electrolyte substantially deriving from the anode compartment, e.g. in the production of sodium hydroxide in which process sodium ions carrying water molecules are transported over the separator. The electrolyte layer is arranged between the separator and the gas diffusion electrode and suitably comprises a carbon cloth, e.g. a graphite cloth, nonwoven cloth filter of fluorinated resins, ceramic fiber cloth, ceramic fluor resin cloth, or a ceramic coated carbon cloth retaining the electrolyte between the gas diffusion electrode and the separator. The carbon cloth suitably extends through the slits made in the cathode members as further described herein. The electrolyte can in this way be drained from the electrolyte layer avoiding flooding of the gas diffusion electrode. The electrolyte can thus leave the cathode compartment in a controlled way at the oxygen-containing gas-supplied side of the cathode compartment.
According to one embodiment, the electrolyte layer is from about 0.1 to about 2 mm thick, preferably from about 0.2 to about 1 mm.
According to one embodiment, the gas diffusion electrode comprises several electrode members. The electrode members are suitably shaped as belts or in patchwork configuration, preferably in patchwork configuration, suitably in which configuration the gas diffusion electrode members are substantially square-shaped. Suitably, the electrode members have a length of from about 2 to about 40 cm, preferably from about 10 to about 30 cm in the vertical direction. If the vertical length is less than about 2 cm, the manufacturing of the electrode members can be complicated. If the vertical length is longer than about 40 cm, the lower portion of the electrode member may be exposed to higher electrolyte pressure than the upper portion, which can reduce the rate of the electrolytic reaction taking place at the gas diffusion electrode member due to difficulties in supplying oxygen-containing gas. The size of the gas diffusion electrode is suitably dimensioned relative to the pressure difference of the electrolyte in the vertical direction. In this way, an optimised homogeneous gas supply can be provided. According to one embodiment, the gas diffusion electrode can pass through the formed slits together with the electrolyte layer. However, even though this embodiment results in extra electrode reaction area, it is preferred that the gas diffusion does not pass through the slits because the extra electrode reaction area will be further away from the separator than the rest of the electrode area which will increase the ohmic loss at said extra electrode reaction area.
Suitably, the gas diffusion electrode members have a length of from about 2 to about 40 cm, preferably from about 10 to about 30 cm in the horizontal direction. The space between adjacent electrode members in the vertical direction may be from about 1 to about 5 mm, preferably from about 2 to about 3 mm.
Preferably, a space is provided between adjacent gas diffusion electrode members in the horizontal direction. Thereby, the gas diffusion electrode members do not necessarily continue over the whole horizontal direction in the cell, but may be divided into plural parts in the horizontal direction. In an embodiment where the electrode members are divided in the horizontal direction, electrolyte can flow down from each space formed by the horizontal division. Thus, electrolyte can easily be released from the electrode members. Preferably, the space between adjacent electrode members in the horizontal direction is from about 1 to about 5 mm, preferably from about 2 to about 3 mm. The structure of plural electrode members arranged both in the horizontal direction and the vertical direction adjacent to each other with a space in between can be described as a patchwork configuration.
The gas diffusion electrode may be a weeping gas diffusion electrode, a semihydrophobic gas diffusion electrode or according to any of the embodiments of gas diffusion electrodes as described in European patent applications No. 01850109.8, No.00850191.8, No.00850219.7 or and U.S. Pat. No. 5,938,901 and U.S. Pat. No. 5,766,429.
According to one embodiment, the method involves arranging resilient means between the existing hydrogen evolving cathode and the gas diffusion electrode. It has been found that resilient means contribute to a more homogeneous contact between the gas diffusion electrode and the electrolyte layer. Furthermore, it has been found that the resilient means can secure safe retention of electrolyte between the separator and the gas diffusion electrode. The resilient means can also play the role of current distributor. Such resilient means may be selected from expanded mesh, wire net, springs, ribs, elastic louvers, perforated plates, metal foams or mixtures thereof, suitably comprising plural members made of a porous metal arranged so that gas and electrolytes thereby easily can be supplied and removed from the gas diffusion electrode. Preferably, the resilient means have substantially the same dimensions as the gas diffusion electrode or plural members thereof so that the resilient means can be individually fitted thereto. The dimensions of the resilient means connected to the gas diffusion electrode are suitably not larger than 40 cm, because the distance to the separator can in those cases be inhomogeneous, which can lead to inhomogeneous current distribution. In case the dimensions are shorter than 10 cm, the manufacturing of the resilient means may be very complicated. The dimensions of the resilient means are suitably from about 10 to about 40 cm, preferably from about 10 to about 30 cm, and most preferably from about 20 to about 25 cm.
The space between the resilient means suitably is from about 1 to about 5 mm, preferably from about 2 to about 3 mm. In case the space is too big, the cell voltage may be too high due to inhomogeneous current distribution in the cell. If the space is too small, the independent adjustments of the electrode members to the resilient means.
The existing cathode being the original hydrogen evolving cathode used in the conventional cell can work as a current distributor in the retrofitted cell.
The invention also relates to a retrofitted electrolytic cell comprising an anode and a cathode compartment, a separator partitioning said compartments, said cathode compartment comprising cathode members having at least one substantially horizontal slit between adjacently vertically arranged cathode members of which at least one is bent away from the separator at the slit, a gas diffusion electrode arranged to at least one of the cathode members on the side facing the separator, and an electrolyte layer arranged to the gas diffusion electrode.
According to one embodiment, the retrofitted electrolytic cell comprises resilient means arranged between the cathode members and the gas diffusion electrode, suitably selected from expanded mesh, wire net, springs, ribs, elastic louvers, metal foams or mixtures thereof.
Suitably, the gas diffusion electrode comprises several electrode members as further described above, suitably arranged in patchwork configuration or belt structure, preferably in patchwork configuration, suitably with square-shaped gas diffusion electrode members.
The electrolyte layer suitably is from about 0.1 to about 2 mm, preferably from about 0.2 to about 1 mm thick.
According to one embodiment, the distance between the slits is from about 100 to about 600 mm, preferably from about 200 to about 400 mm.
Further embodiments and specifications of the retrofitted gas diffusion electrode cell are described in the detailed method for retrofitting the cell.
The invention further relates to the use of the retrofitted electrolytic cell described herein for production of e.g. hydrogen peroxide, alkali metal hydroxide such as KOH and/or NaOH, but may also be used for production of e.g. Na2SO4, HCl, preferably alkali metal hydroxide.